U.S. patent number 10,907,068 [Application Number 16/349,849] was granted by the patent office on 2021-02-02 for cell membrane-mimicking brush polymer and method for preparding same.
This patent grant is currently assigned to CEKO CO., LTD., POSTECH ACADEMY-INDUSTRY FOUNDATION. The grantee listed for this patent is CEKO CO., LTD., POSTECH ACADEMY-INDUSTRY FOUNDATION. Invention is credited to Chang-Sub Kim, Hong-Chul Kim, Hyun-Joong Kim, Jeong-Rae Kim, Kyung-Ho Kwon, Jong-Chan Lee, Moon-Hor Ree.
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United States Patent |
10,907,068 |
Ree , et al. |
February 2, 2021 |
Cell membrane-mimicking brush polymer and method for preparding
same
Abstract
The present invention relates to a cell membrane-mimicking brush
polymer having surface properties mimicking a cell membrane and a
self-assembly capability by means of a cell membrane mimicking
functional group introduced to a brush terminal, and a method for
preparing same.
Inventors: |
Ree; Moon-Hor
(Gyeongsangbuk-do, KR), Kwon; Kyung-Ho (Daegu,
KR), Lee; Jong-Chan (Jeollanam-do, KR),
Kim; Chang-Sub (Chungcheongnam-do, KR), Kim;
Hyun-Joong (Seoul, KR), Kim; Hong-Chul (Seoul,
KR), Kim; Jeong-Rae (Seoul, KR) |
Applicant: |
Name |
City |
State |
Country |
Type |
CEKO CO., LTD.
POSTECH ACADEMY-INDUSTRY FOUNDATION |
Gyeonggi-do
Gyeongsangbuk-do |
N/A
N/A |
KR
KR |
|
|
Assignee: |
CEKO CO., LTD. (Gyeonggi-do,
KR)
POSTECH ACADEMY-INDUSTRY FOUNDATION (Gyeongsangbuk-do,
KR)
|
Family
ID: |
1000005334950 |
Appl.
No.: |
16/349,849 |
Filed: |
November 7, 2017 |
PCT
Filed: |
November 07, 2017 |
PCT No.: |
PCT/KR2017/012538 |
371(c)(1),(2),(4) Date: |
May 14, 2019 |
PCT
Pub. No.: |
WO2018/088775 |
PCT
Pub. Date: |
May 17, 2018 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20190276701 A1 |
Sep 12, 2019 |
|
Foreign Application Priority Data
|
|
|
|
|
Nov 14, 2016 [KR] |
|
|
10-2016-0151218 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
G01N
33/15 (20130101); C08G 65/26 (20130101); C09D
171/00 (20130101); G01N 33/5076 (20130101); G01N
33/92 (20130101); C09D 171/08 (20130101); G01N
33/54393 (20130101) |
Current International
Class: |
C09D
171/08 (20060101); G01N 33/50 (20060101); G01N
33/15 (20060101); G01N 33/92 (20060101); C09D
171/00 (20060101); G01N 33/543 (20060101); C08G
65/26 (20060101) |
Foreign Patent Documents
|
|
|
|
|
|
|
10-0798596 |
|
Jan 2008 |
|
KR |
|
10-0934125 |
|
Dec 2009 |
|
KR |
|
10-2010-0078325 |
|
Jul 2010 |
|
KR |
|
10-2010-0093404 |
|
Aug 2010 |
|
KR |
|
10-2015-0080424 |
|
Jul 2015 |
|
KR |
|
Other References
International Search Report from corresponding PCT Application No.
PCT/KR2017/012538, dated Feb. 8, 2018, with English translation.
cited by applicant.
|
Primary Examiner: Fang; Shane
Attorney, Agent or Firm: Harness, Dickey & Pierce,
P.L.C.
Claims
What is claimed is:
1. A brush polymer compound comprising a structure represented by
the following Formula 1: ##STR00028## wherein, R.sub.1, R.sub.2,
R.sub.4, R.sub.5 and R.sub.6 are independently hydrogen or an alkyl
group having 1 to 20 carbon atoms; R.sub.3 is an alkylene having 1
to 20 carbon atoms; .rho. is an integer of 0 to 20; m and n
represent the content (mol %) of the polyether unit,
0.ltoreq.m.ltoreq.100, 0.ltoreq.n.ltoreq.100 and m+n=100; Y is H,
--CH.sub.2X (wherein X is F, Cl, Br or I), an alkyl group having 1
to 20 carbon atoms, UR.sub.3N.sup..sym.[R.sub.4R.sub.5R.sub.6] or
--ZW; Z and U are linkers connecting the terminal functional group
and the polyether backbone; W is a carbocyclic group of the Formula
2 comprising E.sub.1 to E.sub.21 and G.sub.1 to G.sub.32; -*
represents the point to be connected to Z; E.sub.1 to E.sub.21 are
independently selected from the group consisting of C, N, O, P and
S; provided that E.sub.4, E.sub.5, E.sub.7, E.sub.8, E.sub.10,
E.sub.13, E.sub.14 and E.sub.15 are not O and S; when any one of
E.sub.1 to E.sub.21 is O or S, G attached thereto is not present;
when any one of E.sub.1 to E.sub.21 is N or P, there is no or at
most one G attached thereto; G.sub.1 to G.sub.32, when present, are
independently selected from the group consisting of --CHO, COOH,
--H, --N.sub.3, --NO.sub.2, --NH.sub.2, --OH, --PO.sub.3H, --SH,
--SO.sub.3H, --CH.sub.3, --C.sub.6H.sub.5 and alkyl group having 1
to 20 carbon atoms, or together form .dbd.O, .dbd.N or .dbd.S with
two G's connected to the same E.
2. The brush polymer compound according to claim 1, wherein Z and U
are independently selected from the group represented by the
following Formula 3: ##STR00029## ##STR00030## ##STR00031## wherein
R is hydrogen or an alkylene group having 1 to 20 carbon atoms.
3. The brush polymer compound according to claim 1, having a weight
average molecular weight of 5,000 to 5,000,000.
4. The brush polymer compound according to claim 1, comprising a
structure represented by the following Formula 4: ##STR00032##
wherein m and n represent the content (mol %) of the polyether
unit, 0.ltoreq.m.ltoreq.100, 0.ltoreq.n.ltoreq.100 and m+n=100.
5. A method for preparing a brush polymer compound, comprising the
steps of: step (1) of preparing a polyether polymer compound
comprising a structure represented by the Formula 6 from the cyclic
monomers of the Formula 5 through cationic ring-opening
polymerization, step (2) of preparing a polymer compound having an
azide group and comprising a structure represented by the Formula 7
from the polyether polymer comprising the structure of the Formula
6 in the step (1) through a halogen substitution reaction in an
organic solvent and step (3) of preparing a brush polymer compound
of the Formula 1 using the azide group of the polymer compound
having an azide group of the step (2) and the cycloaddition
reaction of the alkyne group of the functional molecule:
##STR00033## in the Formulas 5 and 6, R.sub.1 and R.sub.2 are
hydrogen or an alkyl group having 1 to 20 carbon atoms, .rho. is an
integer of 0 to 20, d is 50 to 50,000, A is hydrogen, an alkyl
group having 1 to 20 carbon atoms or --CH.sub.2X (wherein X is F,
Cl, Br or I), ##STR00034## in the Formula 7, R.sub.1 and R.sub.2
are hydrogen or an alkyl group having 1 to 20 carbon atoms, .rho.
is an integer of 0 to 20, d is 50 to 50,000 and A' is H,
--CH.sub.2N.sub.3 or an alkyl group having 1 to 20 carbon atoms,
##STR00035## wherein, R.sub.1, R.sub.2, R.sub.4, R.sub.5 and
R.sub.6 are independently hydrogen or an alkyl group having 1 to 20
carbon atoms; R.sub.3 is an alkylene having 1 to 20 carbon atoms;
.rho. is an integer of 0 to 20; m and n represent the content (mol
%) of the polyether unit, 0.ltoreq.m.ltoreq.100,
0.ltoreq.n.ltoreq.100 and m+n=100; Y is H, --CH.sub.2X (wherein X
is F, Cl, Br or I), an alkyl group having 1 to 20 carbon atoms,
UR.sub.3N.sup.61[R.sub.4R.sub.5R.sub.6] or --ZW; Z and U are
linkers connecting the terminal functional group and the polyether
backbone; W is a carbocyclic group of the Formula 2 comprising
E.sub.1 to E.sub.21 and G.sub.1 to G.sub.32; -* represents the
point to be connected to Z; E.sub.1 to E.sub.21 are independently
selected from the group consisting of C, N, O, P and S; provided
that E.sub.4, E.sub.5, E.sub.7, E.sub.8, E.sub.10, E.sub.13,
E.sub.14 and E.sub.15 are not O and S; when any one of E.sub.1 to
E.sub.21 is O or S, G attached thereto is not present; when any one
of E.sub.1 to E.sub.21 is N or P, there is no or at most one G
attached thereto; G.sub.1 to G.sub.32, when present, are
independently selected from the group consisting of --CHO, COOH,
--H, --N.sub.3, --NO.sub.2, --NH.sub.2, --OH, --PO.sub.3H, --SH,
--SO.sub.3H, --CH.sub.3, --C.sub.6H.sub.5 and alkyl group having 1
to 20 carbon atoms, or together form .dbd.O, .dbd.N or .dbd.S with
two G's connected to the same E; and the functional molecule
comprises UR.sub.3N.sup..sym.[R.sub.4R.sub.5R.sub.6] or --ZW at
either end, and comprises an alkyne group at the opposite end.
6. A polymer thin film comprising the brush polymer compound
according to claim 1.
7. A method for preparing a polymer thin film, which comprises a
step of coating a brush polymer compound of claim 1 on a
substrate.
8. The method for preparing a polymer thin film according to claim
7, wherein the coating is performed by any one method selected from
the group consisting of spin coating, spray coating, electrostatic
coating, dip coating, blade coating, ink jet coating and roll
coating.
9. The method according to claim 7, comprising a step of heat
treating the substrate coated with the brush polymer compound under
vacuum at 30 to 100.degree. C. for 10 to 20 hours.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national phase application of PCT Application
No. PCT/KR2017/012538, filed on Nov. 7, 2017, which claims the
benefit and priority to Korean Patent Application No.
10-2016-0151218, filed on Nov. 14, 2016. The entire disclosures of
the applications identified in this paragraph are incorporated
herein by references.
FIELD
The present invention relates to a cell membrane-mimicking brush
polymer and a method for preparing the same.
BACKGROUND
Research on the introduction of functional molecules targeting
biocompatibility, specific molecules, proteins and cells through
various polymer materials mimicking cell membranes and surface
control methods is actively under way. Particularly, in the case of
protein adsorption experiments using the surface plasmon resonance
method, a method using self-assembled monolayers (SAMs) is most
widely used. SAMs can realize desired surface characteristics by
introducing monomolecules having self-assembling properties onto
the substrate surface. In particular, it has been applied to
biosensor research for tracking specific molecules and proteins,
and research of a surface having biocompatibility using
monomolecules having various biomolecules.
However, since SAMs have limitations on chemical stability and
structure, they have a fatal problem in deepening research and
applications.
DISCLOSURE
Technical Purpose
The purpose of the present invention is to provide a cell
membrane-mimicking brush polymer having a self-assembly capability
and surface properties mimicking a cell membrane by using a cell
membrane-mimicking functional group introduced to a brush terminal,
and a method for preparing the same.
Technical Solution
In order to achieve the technical purpose, the present invention
provides a brush polymer compound comprising a structure
represented by the following Formula 1:
##STR00001## wherein, R.sub.1, R.sub.2, R.sub.4, R.sub.5 and
R.sub.6 are independently hydrogen or an alkyl group having 1 to 20
carbon atoms; R.sub.3 is an alkylene having 1 to 20 carbon atoms;
.rho. is an integer of 0 to 20; m and n represent the content (mol
%) of the polyether unit, 0.ltoreq.m.ltoreq.100,
0.ltoreq.n.ltoreq.100 and m+n=100; Y is H, --CH.sub.2X (wherein X
is F, Cl, Br or I), an alkyl group having 1 to 20 carbon atoms,
UR.sub.3N.sup..sym.[R.sub.4R.sub.5R.sub.6] or --ZW; Z and U are
linkers connecting the terminal functional group and the polyether
backbone; W is a carbocyclic group of the Formula 2 comprising
E.sub.1 to E.sub.21 and G.sub.1 to G.sub.32; -* represents the
point to be connected to Z; E.sub.1 to E.sub.21 are independently
selected from the group consisting of C, N, O, P and S; provided
that E.sub.4, E.sub.5, E.sub.7, E.sub.8, E.sub.10, E.sub.13,
E.sub.14 and E.sub.15 are not O and S; when any one of E.sub.1 to
E.sub.21 is O or S, G attached thereto is not present; when any one
of E.sub.1 to E.sub.21 is N or P, there is no or at most one G
attached thereto; G.sub.1 to G.sub.32, when present, are
independently selected from the group consisting of --CHO, COOH,
--H, --N.sub.3, --NO.sub.2, --NH.sub.2, --OH, --PO.sub.3H, --SH,
--SO.sub.3H, --CH.sub.3, --C.sub.6H.sub.5 and alkyl group having 1
to 20 carbon atoms, or together form .dbd.O, .dbd.N or .dbd.S with
two G's connected to the same E.
In the second aspect, the present invention provides a method for
preparing a brush polymer compound, comprising the steps of: step
(1) of preparing a polyether polymer compound comprising a
structure represented by the Formula 6 from the cyclic monomers of
the Formula 5 through cationic ring-opening polymerization, step
(2) of preparing a polymer compound having an azide group and
comprising a structure represented by the Formula 7 from the
polyether polymer comprising the structure of the Formula 6 in the
step (1) through a halogen substitution reaction in an organic
solvent and step (3) of preparing a brush polymer compound of the
Formula 1 using the azide group of the polymer compound having an
azide group of the step (2) and the cycloaddition reaction of the
alkyne group of the functional molecule:
##STR00002##
in the Formulas 5 and 6, R.sub.1 and R.sub.2 are hydrogen or an
alkyl group having 1 to 20 carbon atoms, .rho. is an integer of 0
to 20, d is 50 to 50,000, A is hydrogen, an alkyl group having 1 to
20 carbon atoms or --CH.sub.2X (wherein X is F, Cl, Br or I),
##STR00003##
in the Formula 7, R.sub.1 and R.sub.2 are hydrogen or an alkyl
group having 1 to 20 carbon atoms, .rho. is an integer of 0 to 20,
d is 50 to 50,000 and A' is H, --CH.sub.2N.sub.3 or an alkyl group
having 1 to 20 carbon atoms,
##STR00004## wherein, R.sub.1, R.sub.2, R.sub.4, R.sub.5 and
R.sub.6 are independently hydrogen or an alkyl group having 1 to 20
carbon atoms; R.sub.3 is an alkylene having 1 to 20 carbon atoms;
.rho. is an integer of 0 to 20; m and n represent the content (mol
%) of the polyether unit, 0.ltoreq.m.ltoreq.100,
0.ltoreq.n.ltoreq.100 and m+n=100; Y is H, --CH.sub.2X (wherein X
is F, Cl, Br or I), an alkyl group having 1 to 20 carbon atoms,
UR.sub.3N.sup..sym.[R.sub.4R.sub.5R.sub.6] or --ZW; Z and U are
linkers connecting the terminal functional group and the polyether
backbone; W is a carbocyclic group of the Formula 2 comprising
E.sub.1 to E.sub.21 and G.sub.1 to G.sub.32; -* represents the
point to be connected to Z; E.sub.1 to E.sub.21 are independently
selected from the group consisting of C, N, O, P and S; provided
that E.sub.4, E.sub.5, E.sub.7, E.sub.8, E.sub.10, E.sub.13,
E.sub.14 and E.sub.15 are not O and S; when any one of E.sub.1 to
E.sub.21 is O or S, G attached thereto is not present; when any one
of E.sub.1 to E.sub.21 is N or P, there is no or at most one G
attached thereto; G.sub.1 to G.sub.32, when present, are
independently selected from the group consisting of --CHO, COOH,
--H, --N.sub.3, --NO.sub.2, --NH.sub.2, --OH, --PO.sub.3H, --SH,
--SO.sub.3H, --CH.sub.3, --C.sub.6H.sub.5 and alkyl group having 1
to 20 carbon atoms, or together form .dbd.O, .dbd.N or .dbd.S with
two G's connected to the same E; and the functional molecule
comprises UR.sub.3N.sup..sym.[R.sub.4R.sub.5R.sub.6] or --ZW at
either end, and comprises an alkyne group at the opposite end.
In the third aspect, the present invention provides a polymer thin
film comprising the above brush polymer compound.
In the fourth aspect, the present invention provides a method for
preparing a polymer thin film, which comprises a step of coating
the above brush polymer compound on a substrate.
In the fifth aspect, the present invention provides a method for
preparing a polyether polymer compound comprising a structure
represented by the Formula 6, comprising a step of conducting a
cationic ring-opening polymerization reaction using the cyclic
monomer of the Formula 5 as a reactant:
##STR00005##
in the Formulas 5 and 6, R.sub.1 and R.sub.2 are hydrogen or an
alkyl group having 1 to 20 carbon atoms, .rho. is an integer of 0
to 20, d is 50 to 50,000, A is hydrogen, an alkyl group having 1 to
20 carbon atoms or --CH.sub.2X (wherein X is F, Cl, Br or I).
In the sixth aspect, the present invention provides a method for
preparing a polymer compound having an azide group and comprising a
structure represented by the Formula 7, comprising a step of
conducting a halogen substitution reaction in an organic solvent
from the polyether polymer comprising the structure of the Formula
6 as a reactant:
##STR00006##
in the Formulas 6 and 7, R.sub.1 and R.sub.2 are hydrogen or an
alkyl group having 1 to 20 carbon atoms, .rho. is an integer of 0
to 20, d is 50 to 50,000, A is hydrogen, an alkyl group having 1 to
20 carbon atoms or --CH.sub.2X (wherein X is F, Cl, Br or I) and A'
is H, --CH.sub.2N.sub.3 or an alkyl group having 1 to 20 carbon
atoms.
Advantageous Effects
According to the present invention, it is possible to overcome the
disadvantages of the SAMs described above and to form an economical
polymer thin film having excellent surface control characteristics,
and to provide a functional polymer substance that inhibits or
prevents adhesion, adsorption and binding of various kinds of
pathogenic bacteria and various blood proteins and platelets, and
at the same time, selectively responds to a specific protein. A
cell membrane-mimicking brush polymer can be capable of efficiently
culturing the cells and micro-organisms, and it may be applied as a
biocompatible material for attaching or separating particular
proteins.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of a method for preparing a polymer thin
film of the present invention.
FIGS. 2A, 2B and 2C is schematic views showing a nanostructure of a
polymer thin film according to an embodiment of the present
invention.
FIG. 3 is a GIWAXS image of a polymer thin film according to an
embodiment of the present invention.
FIG. 4 is a graph showing protein adsorption using a surface
plasmon resonance method of a polymer thin film according to an
embodiment of the present invention.
FIG. 5 is a graph showing pneumolysin adsorption using a surface
plasmon resonance method of a polymer thin film according to an
embodiment of the present invention.
DETAILED DESCRIPTION
The present invention will be described in detail in below.
A brush polymer compound of the present invention comprises a
structure represented by the following Formula 1. Since it has a
cell membrane-mimicking functional group introduced to a brush
terminal, it is possible to overcome the disadvantages of the SAMs
described above and to form an economical polymer thin film having
excellent surface control characteristics, and to provide a
functional polymer substance that inhibits or prevents adhesion,
adsorption and binding of various kinds of pathogenic bacteria and
various blood proteins and platelets, and at the same time,
selectively responds to a specific protein.
##STR00007##
wherein,
R.sub.1, R.sub.2, R.sub.4, R.sub.5 and R.sub.6 are independently
hydrogen or an alkyl group having 1 to 20 carbon atoms, and
preferably the alkyl group having 1 to 20 carbon atoms may be an
alkyl group having 1 to 15 carbon atoms, more preferably an alkyl
group having 1 to 10 carbon atoms. R.sub.3 is an alkylene having 1
to 20 carbon atoms, preferably having 1 to 15 carbon atoms, and
more preferably having 1 to 10 carbon atoms.
.rho. is an integer of 0 to 20, preferably an integer of 0 to 15,
and more preferably an integer of 0 to 10.
m and n represent the content (mol %) of the polyether unit,
0.ltoreq.m.ltoreq.100, 0.ltoreq.n.ltoreq.100 and m+n=100; Y is H,
--CH.sub.2X (wherein X is F, Cl, Br or I), an alkyl group having 1
to 20 carbon atoms (preferably having 1 to 15 carbon atoms, and
more preferably having 1 to 10 carbon atoms),
UR.sub.3N.sup..sym.[R.sub.4R.sub.5R.sub.6] or --ZW; Z and U are
linkers connecting the terminal functional group and the polyether
backbone; W is a carbocyclic group of the Formula 2 comprising
E.sub.1 to E.sub.21 and G.sub.1 to G.sub.32; -* represents the
point to be connected to Z; E.sub.1 to E.sub.21 are independently
selected from the group consisting of C, N, O, P and S; provided
that E.sub.4, E.sub.5, E.sub.7, E.sub.8, E.sub.10, E.sub.13,
E.sub.14 and E.sub.15 are not O and S; when any one of E.sub.1 to
E.sub.21 is O or S, G attached thereto is not present; when any one
of E.sub.1 to E.sub.21 is N or P, there is no or at most one G
attached thereto; G.sub.1 to G.sub.32, when present, are
independently selected from the group consisting of --CHO, COOH,
--H, --N.sub.3, --NO.sub.2, --NH.sub.2, --OH, --PO.sub.3H, --SH,
--SO.sub.3H, --CH.sub.3, --C.sub.6H.sub.5 and alkyl group having 1
to 20 carbon atoms (preferably having 1 to 15 carbon atoms, and
more preferably having 1 to 10 carbon atoms), or together form
.dbd.O, .dbd.N or .dbd.S with two G's connected to the same E.
Z and U are linkers connecting the terminal functional group and
the polyether backbone; and are independently selected from the
group represented by the following Formula 3:
##STR00008## ##STR00009## ##STR00010##
wherein R is hydrogen or an alkylene group having 1 to 20 carbon
atoms (preferably having 1 to 15 carbon atoms, and more preferably
having 1 to 10 carbon atoms).
The brush polymer compound of the present invention may have a
weight average molecular weight of 5,000 to 5,000,000, preferably
5,000 to 500,000. When the weight average molecular weight is too
small, there is a problem in the stability of the polymer thin
film. On the other hand, when the weight average molecular weight
is too large, there is a problem in solubility in an organic
solvent.
In one embodiment of the present invention, the brush polymer
compound is a poly
[oxy(4-(14-cholenoatenonyl)-1,2,3-triazol-1-methyl)ethylene-lan-ox-
y(4-(14-phosphorylcolynylnonyl)-1,2,3-triazol-1-methyl)ethylene]
(hereinafter abbreviated as PGA-CholmPCn), comprising a structure
represented by the following Formula 4:
##STR00011##
wherein m and n represent the content (mol %) of the polyether
unit, 0.ltoreq.m.ltoreq.100, 0.ltoreq.n.ltoreq.100 and m+n=100.
In another aspect, the present invention provides a method for
preparing a brush polymer compound, comprising the steps of: step
(1) of preparing a polyether polymer compound comprising a
structure represented by the Formula 6 from the cyclic monomers of
the Formula 5 through cationic ring-opening polymerization, step
(2) of preparing a polymer compound having an azide group and
comprising a structure represented by the Formula 7 from the
polyether polymer comprising the structure of the Formula 6 in the
step (1) through a halogen substitution reaction in an organic
solvent and step (3) of preparing a brush polymer compound of
Formula 1 using the azide group of the polymer compound having an
azide group of the step (2) and the cycloaddition reaction of the
alkyne group of the functional molecule:
##STR00012## in the Formulas 5 and 6, R.sub.1 and R.sub.2 are
hydrogen or an alkyl group having 1 to 20 carbon atoms, .rho. is an
integer of 0 to 20, d is 50 to 50,000, A is hydrogen, an alkyl
group having 1 to 20 carbon atoms or --CH.sub.2X (wherein X is F,
Cl, Br or I),
##STR00013## in the Formula 7, R.sub.1 and R.sub.2 are hydrogen or
an alkyl group having 1 to 20 carbon atoms, .rho. is an integer of
0 to 20, d is 50 to 50,000 and A' is H, --CH.sub.2N.sub.3 or an
alkyl group having 1 to 20 carbon atoms,
##STR00014## wherein, R.sub.1, R.sub.2, R.sub.4, R.sub.5 and
R.sub.6 are independently hydrogen or an alkyl group having 1 to 20
carbon atoms; R.sub.3 is an alkylene having 1 to 20 carbon atoms;
.rho. is an integer of 0 to 20; m and n represent the content (mol
%) of the polyether unit, 0.ltoreq.m.ltoreq.100,
0.ltoreq.n.ltoreq.100 and m+n=100; Y is H, --CH.sub.2X (wherein X
is F, Cl, Br or I), an alkyl group having 1 to 20 carbon atoms,
UR.sub.3N.sup..sym.[R.sub.4R.sub.5R.sub.6] or --ZW; Z and U are
linkers connecting the terminal functional group and the polyether
backbone; W is a carbocyclic group of the Formula 2 comprising
E.sub.1 to E.sub.21 and G.sub.1 to G.sub.32; -* represents the
point to be connected to Z; E.sub.1 to E.sub.21 are independently
selected from the group consisting of C, N, O, P and S; provided
that E.sub.4, E.sub.5, E.sub.7, E.sub.8, E.sub.10, E.sub.13,
E.sub.14 and E.sub.15 are not O and S; when any one of E.sub.1 to
E.sub.21 is O or S, G attached thereto is not present; when any one
of E.sub.1 to E.sub.21 is N or P, there is no or at most one G
attached thereto; G.sub.1 to G.sub.32, when present, are
independently selected from the group consisting of --CHO, COOH,
--H, --N.sub.3, --NO.sub.2, --NH.sub.2, --OH, --PO.sub.3H, --SH,
--SO.sub.3H, --CH.sub.3, --C.sub.6H.sub.5 and alkyl group having 1
to 20 carbon atoms, or together form .dbd.O, .dbd.N or .dbd.S with
two G's connected to the same E; and the functional molecule
comprises UR.sub.3N.sup..sym.[R.sub.4R.sub.5R.sub.6] or --ZW at
either end, and comprises an alkyne group at the opposite end.
In step (1), a polyether polymer compound comprising a structure
represented by the Formula 6 can be prepared from the cyclic
monomers of the Formula 5 through cationic ring-opening
polymerization. The polyether polymer compound comprising a
structure represented by the Formula 6 is an intermediate
synthesized in the process of preparing the brush polymer compound
of the present invention. Although not particularly limited, the
cationic ring-opening polymerization reaction is a polymerization
process through ring-opening reaction of epichlorohydrin, which is
a cyclic monomer using triphenylcarbenium hexafluorophosphate
(TCHP) as an initiator, and the reaction may be carried out by
stirring the reactants in a nitrogen atmosphere for 40 to 50
hours.
In one embodiment of the present invention, the polyether polymer
compound comprising a structure represented by the Formula 6 can be
prepared by a known method and may be prepared by conducting the
cationic ring-opening polymerization reaction in the presence of a
cationic initiator such as triphenylcarbenium hexafluorophosphate,
triphenylcarbenium hexachloroantimonate, alkylaluminum or etc.
##STR00015##
in the Formulas 5 and 6, R.sub.1 and R.sub.2 are hydrogen or an
alkyl group having 1 to 20 carbon atoms (preferably having 1 to 15
carbon atoms, and more preferably having 1 to 10 carbon atoms),
.rho. is an integer of 0 to 20, d is 50 to 50,000, A is hydrogen,
an alkyl group having 1 to 20 carbon atoms (preferably having 1 to
15 carbon atoms, and more preferably having 1 to 10 carbon atoms)
or --CH.sub.2X (wherein X is F, Cl, Br or I).
In step (2), a polymer compound having an azide group and
comprising a structure represented by the Formula 7 can be prepared
from the polyether polymer comprising the structure of the Formula
6 in the step (1) through a halogen substitution reaction in an
organic solvent. The polymer compound having an azide group and
comprising a structure represented by the Formula 7 is an
intermediate synthesized in the process of preparing the brush
polymer compound of the present invention.
In one embodiment of the present invention, the halogen
substitution reaction can introduce an azide (--N3) group by
reacting a CH2X group with sodium azide (NaN3). Examples of the
organic solvent include, but are not limited to, dimethylacetamide,
dimethylformamide or a mixed solution thereof.
The reaction in step (2) may be conducted at a temperature of -100
to 100.degree. C. and a pressure of 1 to 5 atm.
##STR00016##
in the Formula 7, R.sub.1 and R.sub.2 are hydrogen or an alkyl
group having 1 to 20 carbon atoms (preferably having 1 to 15 carbon
atoms, and more preferably having 1 to 10 carbon atoms), .rho. is
an integer of 0 to 20, d is 50 to 50,000 and A' is H,
--CH.sub.2N.sub.3 or an alkyl group having 1 to 20 carbon atoms
(preferably having 1 to 15 carbon atoms, and more preferably having
1 to 10 carbon atoms).
In step (3), a brush polymer compound of Formula 1 can be prepared
using the azide group of the polymer compound having an azide group
of the step (2) and the cycloaddition reaction of the alkyne group
of the functional molecule.
The functional molecule used in the cycloaddition reaction
comprises UR3N.sym.[R4R5R6] or --ZW at either end, and comprises an
alkyne group at the opposite end, wherein R.sub.4, R.sub.5 and
R.sub.6 are independently hydrogen or an alkyl group having 1 to 20
carbon atoms (preferably having 1 to 15 carbon atoms, and more
preferably having 1 to 10 carbon atoms); R.sub.3 is an alkylene
having 1 to 20 carbon atoms (preferably having 1 to 15 carbon
atoms, and more preferably having 1 to 10 carbon atoms); Z and U
are linkers connecting the terminal functional group and the
polyether backbone; W is a carbocyclic group of the Formula 2
comprising E.sub.1 to E.sub.21 and G.sub.1 to G.sub.32; -*
represents the point to be connected to Z; E.sub.1 to E.sub.21 are
independently selected from the group consisting of C, N, O, P and
S; provided that E.sub.4, E.sub.5, E.sub.7, E.sub.8, E.sub.10,
E.sub.13, E.sub.14 and E.sub.15 are not O and S; when any one of
E.sub.1 to E.sub.21 is O or S, G attached thereto is not present;
when any one of E.sub.1 to E.sub.21 is N or P, there is no or at
most one G attached thereto; G.sub.1 to G.sub.32, when present, are
independently selected from the group consisting of --CHO, COOH,
--H, --N.sub.3, --NO.sub.2, --NH.sub.2, --OH, --PO.sub.3H, --SH,
--SO.sub.3H, --CH.sub.3, --C.sub.6H.sub.5 and alkyl group having 1
to 20 carbon atoms, or together form .dbd.O, .dbd.N or .dbd.S with
two G's connected to the same E.
##STR00017##
The cycloaddition reaction (Cu(I)-Catalyzed Azide-Alkyne
Cycloaddition) is a cycloaddition reaction of azide and alkyne
groups. As the solvent, dimethylacetamide, dimethylformamide,
diethyl ether, dichloromethane, tetrahydrofuran or a mixed solution
thereof may be used, but the present invention is not limited
thereto.
Another aspect of the present invention provides a polymer thin
film comprising the above brush polymer compound. Another aspect of
the present invention provides a method for preparing a polymer
thin film, which comprises a step of coating the above brush
polymer compound on a substrate.
The brush polymer compound may be coated by any method selected
from the group consisting of spin coating, spray coating,
electrostatic coating, dip coating, blade coating, ink jet coating
and roll coating.
The method for preparing a polymer thin film of the present
invention comprises a step of heat treating the substrate coated
with the brush polymer compound under vacuum at 30 to 100.degree.
C. for 10 to 20 hours. When out of the above temperature and time
range, there is a problem in the decomposition of the polymer thin
film and formation of a suitable nano-structure. At a high
temperature outside the above range, decomposition of the polymer
thin film may occur, and at low temperatures, there may be problems
in formation of nanostructures.
BEST MODE
The present invention will be described in more detail through the
Examples. However, these Examples are only intended to describe the
present invention exemplarily, and the protected circumstances of
the present invention are not at all limited by them.
EXAMPLE
1. Preparation of a Polyether Polymer Compound Comprising a
Structure Represented by the Formula 6 (Synthesis Example 1)
##STR00018##
40 mL (512 mmol) of epichlorohydrin was added to a 100 mL round
bottom flask and cooled to 5.degree. C. under a nitrogen
atmosphere. A solution of 2.56 mmol of the initiator in
dichloromethane was added thereto, followed by stirring at room
temperature for 4 days. This reactant was dissolved in a small
amount of dichloromethane, reprecipitated in methanol to be
purified, and then was dried at 40.degree. C. under vacuum for 8
hours to prepare polyepichlorohydrin, which is a polyether polymer
compound comprising a structure represented by the Formula 6.
Yield: 65%. .sup.1H-NMR (300 MHz, CDCl.sub.3):
.delta.(ppm)=3.89-3.49 (br, 5H, --OCH--, --OCH.sub.2--,
--CH.sub.2Cl); .sup.13C-NMR (75 MHz, CDCl.sub.3):
.delta.(ppm)=79.70, 70.32, 44.31; FTIR(in film):v(cm.sup.-1)=2960,
2915, 2873, 1427, 1348, 1299, 1263, 1132, 750, 707.
2. Preparation of a Polymer Compound Having an Azide Group and
Comprising a Structure Represented by the Formula 7 (Synthesis
Example 2)
##STR00019##
2.10 g (32.4 mmol) of sodium azide was added to a solution of 1.0 g
(10.8 mmol) of the polyepichlorohydrin compound obtained from
Synthesis Example 1 in 40 mL of dimethylformamide. The mixture was
stirred at 90.degree. C. for 24 hours, and dimethylformamide was
removed by heating under reduced pressure. The remaining solution
was extracted with chloroform, washed with water to remove the
solvent, and then the solvent was removed by heating under reduced
pressure. This polymer substance was dried under vacuum at
40.degree. C. for 8 hours to obtain poly(glycidyl azide) (PGA)
which is the target compound (polymer compound having an azide
group and comprising a structure represented by the Formula 7).
Yield: 90%. .sup.1H-NMR (300 MHz, CDCl.sub.3):
.delta.(ppm)=3.78-3.63 (br, --OCH--, --OCH.sub.2--), 3.50-3.32 (m,
--CH.sub.2N.sub.3); .sup.13C-NMR (75 MHz, CDCl.sub.3):
.delta.(ppm)=79.70, 69.60, 51.80;
3. Preparation of a Functional Molecule 1 (Synthesis Example 3)
##STR00020##
1.00 g (5.94 mmol) of 10-undecyn-1-ol and 2.17 g (6.54 mmol) of
carbon tetrabromide were dissolved in dichloromethane (5 mL)
together in a 100 mL round bottom flask, then 1.72 g (6.54 mmol) of
triphenylphosphine was dissolved in dichloromethane (2 mL) and
slowly added thereto. After stirring at room temperature for 1
hour, the reaction was terminated and the solvent was poured into
cyclohexane. When precipitates were formed, the solvent was removed
through a filter, and the solvent was removed by heating under
reduced pressure. The remaining solution was purified by silica gel
chromatography (50:1 of cyclohexane and ethyl acetate) to obtain
11-bromoundec-1-yne. Yield: 70%. .sup.1H-NMR (300 MHz, CDCl.sub.3):
.delta.(ppm)=3.42 (t, 2H), 2.20 (m, 2H), 1.96 (t, 1H), 1.87 (m,
2H), 1.60-1.25 (br, 12H).
##STR00021##
1.00 g (2.67 mmol) of 3-beta-hydroxy-delta 5-cholenic acid was
dissolved in dimethylformamide (4 mL), then 1.30 g (4.00 mmol) of
cesium carbonate was added and the mixture was stirred at room
temperature for 1 hour. 4.01 g (16.7 mmol) of 11-bromoundec-1-yne
was added thereto, and the mixture was stirred at room temperature
for 20 hours. After the reaction was completed, chloroform (50 mL)
was added thereto and extracted with 0.1 M HCl solution. The
extracted organic solvent was dehydrated by using magnesium
sulfite, and the solvent was removed by heating under reduced
pressure. The resulting material was purified by silica gel
chromatography (3:7 of ethyl acetate and hexane) to obtain
1-cholenoate-10-undecyne (functional molecule 1). Yield: 70%.
.sup.1H-NMR (300 MHz, CDCl.sub.3): .delta.(ppm)=5.36 (m, 1H), 4.04
(t, 2H), 3.53 (m, 1H), 2.44-2.10 (m, 6H), 2.05-1.91 (m, 7H),
1.68-0.79 (m, 35H), 0.67 (s, 3H).
4. Preparation of a Functional Molecule 2 (Synthesis Example 4)
##STR00022##
1.00 g (5.94 mol) of 10-undecyn-1-ol and 0.99 mL (6.54 mmol) of
triethylamine were added to 10 mL of acetonitrile in a 100 mL round
bottom flask, then the solution was cooled and stirred at 0.degree.
C. for 1 hour. 0.60 mL (6.54 mmol) of
2-chloro-2-oxa-1,3,2-dioxaphospholane was slowly added thereto, and
the mixture was stirred at room temperature for 6 hours. After the
completion of the reaction, the resulting precipitate was removed
through a filter, and the remaining solution was cooled to
0.degree. C. 1.76 g (30.0 mmol) of trimethylamine was added thereto
and stirred at 60.degree. C. for 24 hours. The reaction solution
was kept frozen at 0.degree. C. for 6 hours to allow precipitation.
The resulting precipitate was collected through a filter, washed
with acetone, and dried to prepare
10-undecynyle-1-phosphorylcholine (functional molecule 2). Yield:
65%. .sup.1H-NMR (300 MHz, CDCl.sub.3): .delta.(ppm)=4.25 (br, 2H),
3.88 (m, 2H), 3.62 (m, 2H), 3.21 (s, 9H), 2.18 (m, 3H), 1.72-1.58
(br, 2H), 1.58-1.20 (br, 12H).
5. Preparation of Brush Polymer Compound (Example 1) (m=100,
n=0)
##STR00023##
100 mg (1.00 N.sub.3 mmol) of the polymer compound (PGA) obtained
from Synthesis Example 2 was dissolved in dimethylsulfoxide (4 mL),
and then 524 mg (1.00 mmol) of 1-cholenoate-10-undecyne was added
thereto and dissolved. 7.2 mg (5 mol %) of copper bromide was added
to the mixture, and the mixture was stirred at 60.degree. C. for 24
hours. After the reaction was completed, the resultant was purified
through an activated alumina filter, dissolved in a small amount of
chloroform, precipitated in cold diethyl ether, and dried. The
resulting precipitate was collected through a filter and
vacuum-dried to obtain a brush polymer compound. .sup.1H NMR (300
MHz, CDCl.sub.3): .delta.=8.00-7.40 (br, 1H, --C.dbd.CH-- in
triazole), 5.36 (m, 1H, --C.dbd.CH--), 4.50-3.10 (br, 5H,
--CH.sub.2CHO--, --CH.sub.2CHO--, --CH.sub.2-Triazole in backbone),
4.04 (m, 2H, --COOCH.sub.2--), 3.53 (m, 1H, --CHOH), 2.65 (m, 2H,
--CH.sub.2-triazole in brush linker), 2.42-2.13 (m, 4H, cholesteric
acid protons, brush linker protons), 2.10-0.86 (m, 41H, cholesteric
acid protons, brush linker protons), 0.71 (s, 3H, --CH.sub.3).
.sup.13C NMR (150 MHz, CDCl.sub.3): .delta.=173.96, 148.22, 141.01,
122.14, 121.34, 77.95, 71.61, 68.78, 64.21, 56.85, 56.02, 50.77,
50.32, 42.46, 42.43, 39.88, 37.39, 36.56, 35.28, 32.03, 31.89,
31.76, 31.37, 31.12, 29.47, 29.38, 29.31, 29.24, 27.99, 25.94,
25.71, 24.23, 21.13, 19.31, 18.35, 11.86.
6. Preparation of Brush Polymer Compound (Example 2) (m=75,
n=25)
##STR00024##
100 mg (1.00 N.sub.3 mmol) of the polymer compound (PGA) obtained
from Synthesis Example 2 was dissolved in a mixed solution (4 mL)
of methanol and chloroform (1:3), then 397 mg (0.75 mmol) of
1-cholenoate-10-undecyne and 84 mg (0.25 mmol) of
10-undecyl-1-phosphorylcholine were added thereto and dissolved in
the solution. To this mixture were added 13 mg (5 mol %) of
CuSO.sub.4.5H.sub.2O and 30 mg (15 mol %) of sodium ascorbate, and
the mixture was stirred at room temperature for 48 hours. After the
reaction was completed, the reaction product was purified through
dialysis and then dissolved in a small amount of
chloroform/methanol mixed solution and precipitated in cold diethyl
ether. The resulting precipitate was collected through a filter and
vacuum-dried to obtain a brush polymer compound. .sup.1H NMR (300
MHz, CD.sub.3OD/CDCl.sub.3): .delta.=8.00-7.40 (br, --C.dbd.CH-- in
triazole), 5.36 (m, --C.dbd.CH--), 4.50-3.10 (br, --CH.sub.2CHO--,
--CH.sub.2CHO--, --CH.sub.2-Triazole in backbone), 4.26 (m,
--POCH.sub.2CH.sub.2N--), 4.04 (m, --COOCH.sub.2--), 3.85 (m,
--CH.sub.2OP--), 3.67 (m, --POCH.sub.2CH.sub.2N--), 3.46 (m,
--CHOH), 3.25 (s, --N(CH.sub.3).sub.3), 2.65 (m,
--CH.sub.2-triazole in brush linker), 2.42-2.13 (m, cholesteric
acid protons, brush linker protons), 2.10-0.85 (m, cholesteric acid
protons, brush linker protons), 0.69 (s, --CH.sub.3). .sup.13C NMR
(150 MHz, CD.sub.3OD/CDCl.sub.3): .delta.=174.81, 148.31, 140.90,
122.82, 121.32, 77.95, 71.13, 68.64, 66.35, 65.79, 64.46, 63.36,
58.86, 56.69, 55.73, 54.07, 50.77, 50.08, 42.31, 41.82, 39.70,
37.23, 36.44, 35.30, 31.84, 31.80, 31.24, 31.11, 30.99, 30.77,
29.50, 29.36, 29.25, 28.58, 28.03, 25.89, 25.77, 25.56, 24.17,
20.99, 19.23, 18.18, 11.74.
7. Preparation of Brush Polymer Compound (Example 3) (m=50,
n=50)
##STR00025##
100 mg (1.00 N.sub.3 mmol) of the polymer compound (PGA) obtained
from Synthesis Example 2 was dissolved in a mixed solution (4 mL)
of methanol and chloroform (1:3), and 262 mg (0.50 mmol) of
1-cholenoate-10-undecyne and 166 mg (0.50 mmol) of
10-undecyl-1-phosphoryl choline were added thereto and dissolved.
To this mixture were added 13 mg (5 mol %) of CuSO.sub.4.5H.sub.2O
and 30 mg (15 mol %) of sodium ascorbate, and the mixture was
stirred at room temperature for 48 hours. After the reaction was
completed, the reaction product was purified through dialysis and
then dissolved in a small amount of chloroform/methanol mixed
solution and precipitated in cold diethyl ether. The resulting
precipitate was collected through a filter and vacuum-dried to
obtain a brush polymer compound. .sup.1H NMR (300 MHz,
CD.sub.3OD/CDCl.sub.3): .delta.=8.00-7.40 (br, --C.dbd.CH-- in
triazole), 5.36 (m, --C.dbd.CH--), 4.50-3.10 (br, --CH.sub.2CHO--,
--CH.sub.2CHO--, --CH.sub.2-Triazole in backbone), 4.26 (m,
--POCH.sub.2CH.sub.2N--), 4.04 (m, --COOCH.sub.2--), 3.85 (m,
--CH.sub.2OP--), 3.67 (m, --POCH.sub.2CH.sub.2N--), 3.46 (m,
--CHOH), 3.25 (s, --N(CH.sub.3).sub.3), 2.65 (m,
--CH.sub.2-triazole in brush linker), 2.42-2.13 (m, cholesteric
acid protons, brush linker protons), 2.10-0.85 (m, cholesteric acid
protons, brush linker protons), 0.69 (s, --CH.sub.3). .sup.13C NMR
(150 MHz, CD.sub.3OD/CDCl.sub.3): .delta.=174.81, 148.31, 140.90,
122.82, 121.32, 77.95, 71.13, 68.64, 66.35, 65.79, 64.46, 63.36,
58.86, 56.69, 55.73, 54.07, 50.77, 50.08, 42.31, 41.82, 39.70,
37.23, 36.44, 35.30, 31.84, 31.80, 31.24, 31.11, 30.99, 30.77,
29.50, 29.36, 29.25, 28.58, 28.03, 25.89, 25.77, 25.56, 24.17,
20.99, 19.23, 18.18, 11.74.
8. Preparation of Brush Polymer Compound (Example 4) (m=25,
n=75)
##STR00026##
100 mg (1.00 N.sub.3 mmol) of the polymer compound (PGA) obtained
from Synthesis Example 2 was dissolved in a mixed solution (4 mL)
of methanol and chloroform (1:3), and then 131 mg (0.25 mmol) of
1-cholenoate-10-undecyne and 250 mg (0.75 mmol) of
10-undecyl-1-phosphoryl choline were added thereto and dissolved in
the solution. To this mixture were added 13 mg (5 mol %) of
CuSO.sub.4.5H.sub.2O and 30 mg (15 mol %) of sodium ascorbate, and
the mixture was stirred at room temperature for 48 hours. After the
reaction was completed, the reaction product was purified through
dialysis and then dissolved in a small amount of
chloroform/methanol mixed solution and precipitated in cold diethyl
ether. The resulting precipitate was collected through a filter and
vacuum-dried to obtain a brush polymer compound. .sup.1H NMR (300
MHz, CD.sub.3OD/CDCl.sub.3): .delta.=8.00-7.40 (br, --C.dbd.CH-- in
triazole), 5.36 (m, --C.dbd.CH--), 4.50-3.10 (br, --CH.sub.2CHO--,
--CH.sub.2CHO--, --CH.sub.2-Triazole in backbone), 4.26 (m,
--POCH.sub.2CH.sub.2N--), 4.04 (m, --COOCH.sub.2--), 3.85 (m,
--CH.sub.2OP--), 3.67 (m, --POCH.sub.2CH.sub.2N--), 3.46 (m,
--CHOH), 3.25 (s, --N(CH.sub.3).sub.3), 2.65 (m,
--CH.sub.2-triazole in brush linker), 2.42-2.13 (m, cholesteric
acid protons, brush linker protons), 2.10-0.85 (m, cholesteric acid
protons, brush linker protons), 0.69 (s, --CH.sub.3). .sup.13C NMR
(150 MHz, CD.sub.3OD/CDCl.sub.3): .delta.=174.81, 148.31, 140.90,
122.82, 121.32, 77.95, 71.13, 68.64, 66.35, 65.79, 64.46, 63.36,
58.86, 56.69, 55.73, 54.07, 50.77, 50.08, 42.31, 41.82, 39.70,
37.23, 36.44, 35.30, 31.84, 31.80, 31.24, 31.11, 30.99, 30.77,
29.50, 29.36, 29.25, 28.58, 28.03, 25.89, 25.77, 25.56, 24.17,
20.99, 19.23, 18.18, 11.74.
9. Preparation of Brush Polymer Compound (Example 5) (n=100)
##STR00027##
100 mg (1.00 N.sub.3 mmol) of the polymer compound (PGA) obtained
from Synthesis Example 2 was dissolved in a mixed solution (4 mL)
of methanol and chloroform (1:3), and then 375 mg (1.00 mmol) of
10-undecynyl-1-phosphorylcholine was added thereto and dissolved.
To this mixture were added 13 mg (5 mol %) of CuSO.sub.4.5H.sub.2O
and 30 mg (15 mol %) of sodium ascorbate, and the mixture was
stirred at room temperature for 48 hours. After the reaction was
completed, the reaction product was purified through dialysis and
then dissolved in a small amount of chloroform/methanol mixed
solution and precipitated in cold diethyl ether. The resulting
precipitate was collected through a filter and vacuum-dried to
obtain a brush polymer compound. .sup.1H NMR (300 MHz,
CD.sub.3OD/CDCl.sub.3): .delta.=8.00-7.40 (br, 1H, --C.dbd.CH-- in
triazole), 4.50-3.10 (br, 5H, --CH.sub.2CHO--, --CH.sub.2CHO--,
--CH.sub.2-Triazole in backbone), 4.26 (m, 2H,
--POCH.sub.2CH.sub.2N--), 3.85 (m, 2H, --CH.sub.2OP--), 3.67 (m,
2H, --POCH.sub.2CH.sub.2N--), 3.25 (s, 9H, --N(CH.sub.3).sub.3),
2.65 (m, 2H, --CH.sub.2-triazole in brush linker), 1.90-0.85 (m,
14H, --(CH.sub.2).sub.7--). .sup.13C NMR (150 MHz,
CD.sub.3OD/CDCl.sub.3): .delta.=148.09, 123.53, 77.79, 76.64,
70.21, 68.70, 66.06, 65.49, 58.97, 53.34, 50.91, 30.62, 29.43,
29.23, 25.65, 25.29.
10. Preparation of Polymer Thin Film
The brush polymeric compounds prepared in Examples 1 to 5 were
dissolved in a mixed solvent of chloroform and methanol (50:50 vol
%) at 1 wt %, and then filtered with a syringe filter of 0.2
microfilter. The solution filtered was spin-coated on the substrate
and heat-treated at 50.degree. C. for 12 hours under vacuum to
prepare a polymer thin film. (If the above conditions are not met,
it is difficult to form a nano-sized polymer thin film, and there
may be problems in formation of nanostructure.)
The nanostructure of the prepared polymer thin film is shown in
FIG. 2, and the grazing incidence wide angle X-ray scattering
(GIWAXS) pattern of a polymer thin film is shown in FIG. 3.
The structure of the thin film has a multibilayer structure (FIG. 2
(a)) at 100% according to the fraction of cholesterol terminal
group, and as the fraction of phosphorylcholine terminal group
increases, the steric hindrance caused by the triazole linker
increases rather than the mutual attraction between the cholesterol
terminal groups, and the brush tends to rotate, which interferes
with the formation of the multibilayer structure. The optimum
fraction for the multibilayer structure was evaluated as 75% of the
cholesterol terminal group and 25% of the phosphorylcholine
terminal group, which means that a certain percentage of the
phosphorylcholine terminal group lowered the density of the bulky
cholesterol terminal group to reduce steric hindrance. The h shown
in FIG. 2 represents the thickness of the layer with a higher
electron density in the multibilayer structure, dr1 denotes the
distance between neighboring brushes connected to one main chain,
and dr2 denotes the distance between adjacent main chains in the
direction parallel to the thin film. FIG. 3 shows a two-dimensional
scattering pattern of grazing incidence wide angle X-ray
scattering, (a) shows a multibilayer structure of repeated patterns
in a direction perpendicular to the thin film, and (b) shows a
structure in which polymer chains lying in a direction parallel to
a thin film are stacked in a cylindrical shape. The fraction of
cholesterol terminal groups increased to 25%, 50%, and 75% from (c)
to (e), and at 75%, scattering patterns are seen at regular
intervals in the direction perpendicular to the film, which
indicates that the multibilayer structure is best formed.
11. Protein Adsorption Experiment
The brush polymeric compounds prepared in Examples 1 to 5 were
dissolved in a mixed solvent of chloroform and methanol (50:50 vol
%) at 1 wt % and then filtered with a syringe filter of 0.2
microfilter. The solution filtered was then spin-coated on a prism
coated with gold and heat-treated at 50.degree. C. for 12 hours
under vacuum. Polymer-coated prisms were tested for adsorption on
four different proteins using surface plasmon resonance
spectroscopy. The concentration of each protein was adjusted to 1
mg/mL, and the change in reflectance according to adsorption is
shown in FIG. 4. The adsorption experiments of Pneumolysin were
also carried out under the same conditions and are shown in FIG.
5.
* * * * *